JP4429756B2 - Filter catalyst - Google Patents
Filter catalyst Download PDFInfo
- Publication number
- JP4429756B2 JP4429756B2 JP2004033924A JP2004033924A JP4429756B2 JP 4429756 B2 JP4429756 B2 JP 4429756B2 JP 2004033924 A JP2004033924 A JP 2004033924A JP 2004033924 A JP2004033924 A JP 2004033924A JP 4429756 B2 JP4429756 B2 JP 4429756B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- slurry
- filter
- pores
- carrier substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 218
- 239000002002 slurry Substances 0.000 claims description 90
- 239000000758 substrate Substances 0.000 claims description 88
- 239000011148 porous material Substances 0.000 claims description 60
- 239000000843 powder Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 23
- 238000010304 firing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 230000000052 comparative effect Effects 0.000 description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- 239000002585 base Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000001238 wet grinding Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 210000002421 cell wall Anatomy 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/007—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore distribution, e.g. inhomogeneous distribution of pores
- C04B38/0074—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore distribution, e.g. inhomogeneous distribution of pores expressed as porosity percentage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Description
本発明は、ディーゼルエンジン等の内燃機関から排出されるガスに含まれている物質のうち少なくともパティキュレートを除去し、排気ガスを浄化するフィルタ触媒に関する。 The present invention relates to a filter catalyst that purifies exhaust gas by removing at least particulates among substances contained in gas discharged from an internal combustion engine such as a diesel engine.
ディーゼルエンジン等の内燃機関から排出される排気ガスには、パティキュレートが含まれている。パティキュレートには、人体に有害な物質が含まれており、これを除去することが環境上の課題となっている。 Particulates are contained in the exhaust gas discharged from an internal combustion engine such as a diesel engine. Particulates contain substances that are harmful to the human body, and removing them is an environmental issue.
パティキュレートの除去には、フィルタ触媒が用いられている。フィルタ触媒は、たとえば、特許文献1〜7に示されている。 A filter catalyst is used to remove the particulates. The filter catalyst is shown by patent documents 1-7, for example.
従来のフィルタ触媒は、連続した細孔を有する多孔質セラミックスよりなる触媒担体基材上にアルミナ等よりなる担持層に触媒金属が担持してなる触媒層を形成した構造を有している。そして、フィルタ触媒は、触媒担体基材の連続した細孔から形成された通気孔を排気ガスが通過するときに、パティキュレートを捕捉する。多孔質セラミックス上に形成された触媒層が捕捉したパティキュレートを分解する。このとき、フィルタ触媒に排気ガスが通過するだけの通気孔が形成されていないと、捕捉したパティキュレートが堆積し、排気ガスの通過時に圧損が生じる。圧損を抑えるために通気孔を大きくすると、パティキュレートを捕捉できなくなる。 A conventional filter catalyst has a structure in which a catalyst layer in which a catalyst metal is supported on a support layer made of alumina or the like is formed on a catalyst support substrate made of porous ceramics having continuous pores. The filter catalyst captures the particulates when the exhaust gas passes through the ventilation holes formed from the continuous pores of the catalyst carrier substrate. The particulates captured by the catalyst layer formed on the porous ceramics are decomposed. At this time, if the vent hole through which the exhaust gas passes is not formed in the filter catalyst, the trapped particulates are accumulated, and pressure loss occurs when the exhaust gas passes. If the air hole is enlarged to suppress the pressure loss, the particulates cannot be captured.
従来のフィルタ触媒においては、触媒担体基材上に形成された触媒層が触媒担体基材の細孔の開口径を狭くして通気孔が十分な開口径を有さなくなったり、通気孔が開口しなくなる(閉塞する)という問題があった。具体的には、フィルタ触媒の触媒層は、アルミナ等を有するスラリーを調製し、このスラリーを触媒担体基材に塗布し、乾燥・焼成することで担持層を形成し、その後触媒金属を担持させることで製造されている。スラリーの触媒担体基材への塗布時には、スラリーが触媒担体基材の細孔の内部にまで十分に分散しないため、触媒担体基材の細孔の開口部近傍に偏って存在するようになっていた。この状態で乾燥・焼成して触媒層が形成されるため、通気孔の開口部の縮径や閉塞が生じ、フィルタ触媒として十分な通気孔が形成できなくなっていた。
本発明は上記実状に鑑みてなされたものであり、触媒層による通気孔の閉塞が抑制されたフィルタ触媒を提供することを課題とする。 This invention is made | formed in view of the said actual condition, and makes it a subject to provide the filter catalyst by which obstruction | occlusion of the vent hole by a catalyst layer was suppressed.
上記課題を解決するために本発明者らはフィルタ触媒について検討を重ねた結果、数μm規模の細孔はパティキュレートを捕捉して堆積させたときに堆積したパティキュレートが圧損を生じさせることに着目し、本発明をなすに至った。 In order to solve the above problems, the present inventors have studied the filter catalyst, and as a result, when the fine pores of several μm are trapped and deposited, the deposited particulate causes pressure loss. Attention was paid to the present invention.
本発明のフィルタ触媒は、連続した細孔を有する耐熱性多孔質体よりなる触媒担体基材と、触媒担体基材の表面上に形成されたパティキュレートを燃焼する触媒層と、を有するフィルタ触媒において、1〜20μmの細孔を11%以上の気孔率で有することを特徴とする。なお、本発明においては、細孔径および気孔率は、水銀圧入法を用いて測定した値を用いた。 The filter catalyst of the present invention is a filter catalyst having a catalyst carrier substrate made of a heat-resistant porous body having continuous pores, and a catalyst layer for burning particulates formed on the surface of the catalyst carrier substrate. In which pores of 1 to 20 μm have a porosity of 11% or more. In the present invention, the pore diameter and the porosity are values measured using a mercury intrusion method.
本発明のフィルタ触媒は、1〜20μmの細孔を11%以上の気孔率で有している。1〜20μmの細孔を有することで捕捉されたパティキュレートが堆積しても圧損を大きく上昇させなくなっている。すなわち、本発明のフィルタ触媒は、十分なパティキュレートが堆積したときの圧損の上昇を抑えることができる効果を有する。 The filter catalyst of the present invention has 1 to 20 μm pores with a porosity of 11% or more. By having 1 to 20 μm pores, even if trapped particulates are deposited, the pressure loss is not greatly increased. That is, the filter catalyst of the present invention has an effect of suppressing an increase in pressure loss when sufficient particulates are deposited.
本発明のフィルタ触媒は、触媒担体基材と、触媒層と、を有する。 The filter catalyst of the present invention has a catalyst carrier substrate and a catalyst layer.
触媒担体基材は、連続した細孔を有する耐熱性多孔質体よりなる。フィルタ触媒において触媒担体基材の連続した細孔から排気ガスが通過する通気孔が形成される。 The catalyst carrier substrate is composed of a heat resistant porous body having continuous pores. In the filter catalyst, vent holes are formed through which exhaust gas passes from continuous pores of the catalyst carrier substrate.
触媒層は、触媒担体基材の表面上に形成されパティキュレートを燃焼する。触媒層がパティキュレートを燃焼することで、フィルタ触媒において捕捉したパティキュレートを除去できる。 The catalyst layer is formed on the surface of the catalyst carrier substrate and burns the particulates. When the catalyst layer burns the particulates, the particulates captured in the filter catalyst can be removed.
本発明のフィルタ触媒は、1〜20μmの細孔を11%以上の気孔率で有する。1〜20μmの細孔を11%以上の気孔率で有することで、圧損を上昇させることなくパティキュレートの捕捉を行うことができ、捕捉したパティキュレートを燃焼できるようになる。 The filter catalyst of the present invention has 1 to 20 μm pores with a porosity of 11% or more. By having 1 to 20 μm pores with a porosity of 11% or more, particulates can be captured without increasing the pressure loss, and the captured particulates can be burned.
具体的には、フィルタ触媒において排気ガスは、フィルタ触媒のセル壁に開口した触媒担体基材の細孔から形成された通気孔を通過する。そしてこのとき、パティキュレートは、触媒層に捕捉される。そして、パティキュレートの捕捉には、特に20μm以下の細孔径の細孔が寄与している。本発明のフィルタ触媒は、細孔径を規制し、1〜20μm以下の径の細孔を11%以上と高い気孔率で有することで、圧損を大幅に上昇させることなくパティキュレートの除去を行うことが可能となっている。 Specifically, in the filter catalyst, the exhaust gas passes through a vent formed from the pores of the catalyst carrier base that opens to the cell wall of the filter catalyst. At this time, the particulates are trapped in the catalyst layer. In particular, pores having a pore diameter of 20 μm or less contribute to particulate capture. The filter catalyst of the present invention regulates the pore diameter and removes particulates without significantly increasing pressure loss by having pores with a diameter of 1 to 20 μm or less at a high porosity of 11% or more. Is possible.
触媒層は、フィルタ触媒において捕捉したパティキュレートを燃焼できるものであれば特に限定されるものではない。触媒層は、耐熱性無機酸化物よりなる担持層と、担持層に担持された触媒金属と、からなることが好ましい。 The catalyst layer is not particularly limited as long as it can burn the particulates captured in the filter catalyst. The catalyst layer is preferably composed of a support layer made of a heat-resistant inorganic oxide and a catalyst metal supported on the support layer.
担持層を形成する耐熱性無機酸化物としては、Al2O3,SiO2,TiO2,ZrO2,CeO2などの遷移金属酸化物、希土類元素酸化物、アルカリ金属酸化物、アルカリ土類金属酸化物やこれらの複合酸化物の一種以上をあげることができる。また、触媒金属としては、Pt,Pd,Rh,Ir,Ag,Au等の貴金属の少なくとも一種をあげることができる。 Examples of the heat-resistant inorganic oxide that forms the support layer include transition metal oxides such as Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , and CeO 2 , rare earth element oxides, alkali metal oxides, and alkaline earth metals. One or more oxides or complex oxides thereof can be given. Moreover, as a catalyst metal, at least 1 type of noble metals, such as Pt, Pd, Rh, Ir, Ag, Au, can be mention | raise | lifted.
触媒層が、耐熱性酸化物粉末のスラリーを調製し、スラリーを触媒担体基材にコートし、乾燥、焼成してなる担持層を有し、スラリーに分散した粉末の全体量を100wt%としたときに、1μm以下の粒径の耐熱性酸化物粉末が70wt%以上で含まれることが好ましい。1μm以下の粒径の耐熱性酸化物粉末が70wt%以上で含まれたスラリーを用いて担持層が形成されたことで、触媒層の通気孔の細孔径を規制することができる。 The catalyst layer has a heat-resistant oxide powder slurry, has a support layer formed by coating the slurry on a catalyst carrier substrate, dried and fired, and the total amount of powder dispersed in the slurry is 100 wt% Sometimes, it is preferable that the heat-resistant oxide powder having a particle size of 1 μm or less is contained at 70 wt% or more. By forming the support layer using the slurry containing 70 wt% or more of the heat-resistant oxide powder having a particle size of 1 μm or less, the pore diameter of the vent hole of the catalyst layer can be regulated.
詳しくは、スラリーを構成する耐熱性酸化物粉末の粒径が規制されることで、触媒担体基材の表面に均一な厚さでスラリーをコートすることが可能となり、このスラリーを乾燥焼成してなる担持層が所定の径の細孔を有することとなる。すなわち、触媒担体基材自体が有している細孔の表面にも触媒層を均一な厚さで形成することができるため、触媒担体基材の細孔を触媒層が閉塞しなくなり、所定の径の細孔を有することとなる。 Specifically, by regulating the particle size of the heat-resistant oxide powder constituting the slurry, it becomes possible to coat the slurry with a uniform thickness on the surface of the catalyst carrier substrate. The resulting support layer has pores of a predetermined diameter. That is, since the catalyst layer can be formed with a uniform thickness on the surface of the pores of the catalyst carrier base material itself, the catalyst layer does not block the pores of the catalyst carrier base material. It will have pores of diameter.
また、触媒担体基材は、触媒層がその表面に形成されるものであり、触媒層を形成したときに所望の細孔径の細孔を形成できる基材であれば特に限定されるものではない。触媒担体基材は、10μm以上の細孔径の細孔を50%以上の気孔率で有することが好ましく、さらに20μm以上の細孔径の細孔を40%以上の気孔率で有することが好ましい。なお、触媒担体基材の細孔の細孔径の上限は、特に限定されるものではないが、過剰に大きくなると触媒層に所望の大きさの細孔径を形成することが困難になる。 Further, the catalyst carrier substrate is not particularly limited as long as the catalyst layer is formed on the surface thereof and can form pores having a desired pore diameter when the catalyst layer is formed. . The catalyst support substrate preferably has pores with a pore diameter of 10 μm or more with a porosity of 50% or more, and further preferably has pores with a pore diameter of 20 μm or more with a porosity of 40% or more. The upper limit of the pore size of the pores of the catalyst carrier substrate is not particularly limited, but if it is excessively large, it becomes difficult to form a pore size having a desired size in the catalyst layer.
また、触媒担体基材は、従来のフィルタ触媒において触媒担体基材として用いられている基材を用いることができる。たとえば、コーディエライト、SiC、その他の耐熱性のセラミックスよりなるウォールフローDPF(ディーゼルパティキュレートフィルタ)、セラミックスフォームフィルタ、メタル不織布DPFを用いることができる。 The catalyst carrier substrate may be a substrate that is used as a catalyst carrier substrate in a conventional filter catalyst. For example, a wall flow DPF (diesel particulate filter) made of cordierite, SiC, or other heat-resistant ceramics, a ceramic foam filter, or a metal nonwoven fabric DPF can be used.
本発明のフィルタ触媒は、触媒担体基材および触媒層を有し、上記構成を有するものであればその材質および製造方法が特に限定されるものではない。 The filter catalyst of the present invention has a catalyst carrier substrate and a catalyst layer, and the material and production method thereof are not particularly limited as long as the filter catalyst has the above-described configuration.
担持層を形成する耐熱性無機酸化物としては、Al2O3,SiO2,TiO2,ZrO2,CeO2などの遷移金属酸化物、希土類元素酸化物、アルカリ金属酸化物、アルカリ土類金属酸化物やこれらの複合酸化物の一種以上をあげることができる。また、触媒金属としては、Pt,Pd,Rh,Ir,Ag,Au等の貴金属の少なくとも一種をあげることができる。 Examples of the heat-resistant inorganic oxide that forms the support layer include transition metal oxides such as Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , and CeO 2 , rare earth element oxides, alkali metal oxides, and alkaline earth metals. One or more oxides or complex oxides thereof can be given. Moreover, as a catalyst metal, at least 1 type of noble metals, such as Pt, Pd, Rh, Ir, Ag, Au, can be mention | raise | lifted.
本発明のフィルタ触媒は、たとえば、以下の製造方法により製造することができる。 The filter catalyst of the present invention can be produced, for example, by the following production method.
まず、担持層の原料となる酸化物からスラリーを調製する。このとき、スラリーを構成する酸化物粒子は、酸化物粒子の全量を100wt%としたときに、1μm以下の粒径の粒子が70wt%以上となるように調製された。 First, a slurry is prepared from an oxide as a raw material for the support layer. At this time, the oxide particles constituting the slurry were prepared such that particles having a particle size of 1 μm or less were 70 wt% or more when the total amount of oxide particles was 100 wt%.
このスラリーを触媒担体基材にコーティングした。触媒担体基材の(見かけの)容積1リットルあたりのコート量(酸化物粒子換算)が、1μm以下の粒径の粒子が70〜90wt%の場合には150g以下が好ましく、90wt%を超えると200g以下であることが好ましい。コート量は、コーティングの前後の重量から求めた。 This slurry was coated on the catalyst support substrate. The coating amount per 1 liter (apparent) volume of the catalyst support substrate (in terms of oxide particles) is preferably 150 g or less when particles having a particle size of 1 μm or less are 70 to 90 wt%, and when the amount exceeds 90 wt% It is preferable that it is 200 g or less. The coating amount was determined from the weight before and after coating.
触媒担体基材へのスラリーのコーティングは、スラリーを触媒担体基材の表面に塗布した後に、余分なスラリーを吹き払うことでなされた。その後、スラリーを乾燥させた後に焼成して担持層を形成した。つづいて、触媒金属水溶液に浸漬、焼成して触媒金属を担持させた。 Coating of the slurry on the catalyst support substrate was performed by blowing off excess slurry after the slurry was applied to the surface of the catalyst support substrate. Thereafter, the slurry was dried and then fired to form a support layer. Subsequently, the catalyst metal was supported by dipping and firing in an aqueous catalyst metal solution.
以上の手順により、本発明のフィルタ触媒を製造することができる。 The filter catalyst of the present invention can be manufactured by the above procedure.
(実施例1)
まず、アルミナ(Al2O3)粉末150g、水200gを秤量し、アルミナ粉末を水に投入、攪拌して分散させ、湿式ミリングを施してスラリーを調製した。アルミナ粉末全体を100wt%としたときに、1μm以下の粒径の粒子が77%となっていた。
Example 1
First, 150 g of alumina (Al 2 O 3 ) powder and 200 g of water were weighed, and the alumina powder was put into water, stirred and dispersed, and wet milled to prepare a slurry. When the entire alumina powder was 100 wt%, particles having a particle size of 1 μm or less were 77%.
つづいて、スラリーを触媒担体基材にコートした。触媒担体基材1は、厚さが300μmのセル壁で区画されたセルを48セル/cm2(約300セル/inch2)で軸方向に有する略円柱状の見かけの容積が35cm3のコーディエライト製の触媒担体基材(株式会社デンソー製)である。この触媒担体基材1は、各セルの両端部に形成された2つの開口部のうち1つは、封止材2によって交互に封止されている。つまり、多数あるセルのうち、約半数のものは一方の端面において開口し、残りのものは他方の端面において開口している。触媒担体基材1の端面において、封止されたセル2と開口したセル3とが交互に並んでいる。従って、触媒担体基材1の端面は、市松模様状になっている。触媒担体基材1を図1に示した。
Subsequently, the slurry was coated on the catalyst support substrate. The
スラリーの触媒担体基材へのコートは、スラリー中に触媒担体基材を浸漬し、引き出した後に過剰なスラリーを除去した後に、乾燥、焼成することで行われた。なお、本実施例において過剰なスラリーの除去は、両端の圧力差が10kPaとなるようにした状態で5〜30秒間保持してスラリーを吸引し、その後、他方の端部側を常圧に戻し5〜30秒間保持する圧力変動を繰り返すことでなされた。この圧力変動は、触媒担体基材に塗布されたスラリーが所定の重量となるまで繰り返された。なお、本実施例の製造時における圧力変動は、両端部のそれぞれの端部側からスラリーの吸引を行ったため2回であった。また、焼成は、500℃で1時間加熱することで行われた。 The coating of the slurry on the catalyst carrier substrate was performed by immersing the catalyst carrier substrate in the slurry, removing the excess slurry after drawing, and then drying and firing. In this embodiment, the excess slurry is removed by holding the slurry for 5 to 30 seconds in a state where the pressure difference between both ends is 10 kPa, and then returning the other end to the normal pressure. This was done by repeating the pressure fluctuation held for 5-30 seconds. This pressure fluctuation was repeated until the slurry applied to the catalyst carrier substrate reached a predetermined weight. In addition, the pressure fluctuation at the time of manufacture of a present Example was twice since the suction of the slurry was performed from each edge part side of both ends. Moreover, baking was performed by heating at 500 degreeC for 1 hour.
スラリーがコートされた触媒担体基材の重さを測定したところ、触媒担体基材の見かけの容積1リットルあたり150gの担持量でアルミナが担持された。 When the weight of the catalyst carrier substrate coated with the slurry was measured, alumina was loaded at a loading amount of 150 g per liter apparent volume of the catalyst carrier substrate.
そして、1.5g/LでPtを含むPt硝酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥した。乾燥は、350℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり3gの担持量でPtが担持された。このPtは、触媒成分としてパティキュレートの燃焼をおこなう。 Then, a Pt nitrate aqueous solution containing Pt at 1.5 g / L was prepared, and the catalyst carrier base material coated with the slurry was immersed, pulled out, and dried. Drying was performed by heating at 350 ° C. for 1 hour. Pt was supported at a supported amount of 3 g per liter of apparent volume of the catalyst support substrate. This Pt burns particulates as a catalyst component.
そして、50g/LでBaを含むBa酢酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥、焼成した。焼成は、500℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり13.7g(0.1mol)の担持量でBaが担持された。なお、このBaは、フィルタ触媒においてはNOx吸蔵成分としてはたらく。 Then, a Ba acetate aqueous solution containing Ba at 50 g / L was prepared, and the catalyst support base material coated with the slurry was immersed, pulled out, dried and fired. Firing was performed by heating at 500 ° C. for 1 hour. Ba was supported at a supported amount of 13.7 g (0.1 mol) per liter of apparent volume of the catalyst support substrate. This Ba acts as a NOx occlusion component in the filter catalyst.
以上の手順により、実施例1のフィルタ触媒が製造された。 The filter catalyst of Example 1 was manufactured by the above procedure.
(実施例2)
アルミナ粉末からなるスラリーに代えて、チタニア粉末(TiO 2 )からなるスラリーを用いたこと以外は、実施例1と同様にして本実施例のフィルタ触媒を製造した。
(Example 2)
A filter catalyst of this example was produced in the same manner as in Example 1 except that a slurry made of titania powder (TiO 2 ) was used instead of the slurry made of alumina powder .
チタニア粉末150g、水200gを秤量し、チタニア粉末を水に投入、攪拌して分散させ、湿式ミリングを施してスラリーを調製した。チタニア粉末全体を100wt%としたときに、1μm以下の粒径の粒子が85%となっていた。 150 g of titania powder and 200 g of water were weighed, and the titania powder was put into water, stirred and dispersed, and wet milling was performed to prepare a slurry. When the total titania powder was 100 wt%, particles having a particle size of 1 μm or less were 85%.
スラリーを実施例1において用いられたものと同じ触媒担体基材にコートした。スラリーの触媒担体基材へのコートは、スラリー中に触媒担体基材を浸漬し、引き出した後に過剰なスラリーを除去した後に、乾燥、焼成することで行われた。なお、本実施例においてスラリーの除去は、両端の圧力差が10kPaとなるようにした状態で5〜30秒間保持してスラリーを吸引し、その後、他方の端部側を常圧に戻し5〜30秒間保持する圧力変動を繰り返すことでなされた。この圧力変動は、触媒担体基材に塗布されたスラリーが所定の重量となるまで繰り返された。なお、本実施例の製造時には、実施例1のときと同様に圧力変動は2回であった。また、焼成は、500℃で1時間加熱することで行われた。 The slurry was coated on the same catalyst support substrate used in Example 1. The coating of the slurry on the catalyst carrier substrate was performed by immersing the catalyst carrier substrate in the slurry, removing the excess slurry after drawing, and then drying and firing. In this example, the slurry is removed by holding the slurry for 5 to 30 seconds with the pressure difference between both ends being 10 kPa , sucking the slurry, and then returning the other end to normal pressure. This was done by repeating the pressure fluctuation held for 30 seconds. This pressure fluctuation was repeated until the slurry applied to the catalyst carrier substrate reached a predetermined weight. In the production of this example, the pressure fluctuation was twice as in the case of Example 1. Moreover, baking was performed by heating at 500 degreeC for 1 hour.
スラリーがコートされた触媒担体基材の重さを測定したところ、スラリーのコート前より5.3g増加していた。すなわち、触媒担体基材の見かけの容積1リットルあたり150gの担持量でチタニアが担持された。 When the weight of the catalyst carrier substrate coated with the slurry was measured, it was increased by 5.3 g from before the slurry was coated. That is, titania was supported at a supported amount of 150 g per liter apparent volume of the catalyst support substrate.
そして、1.5g/LでPtを含むPt硝酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥した。乾燥は、350℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり3gの担持量でPtが担持された。このPtは、触媒成分としてパティキュレートの燃焼をおこなう。 Then, a Pt nitrate aqueous solution containing Pt at 1.5 g / L was prepared, and the catalyst carrier base material coated with the slurry was immersed, pulled out, and dried. Drying was performed by heating at 350 ° C. for 1 hour. Pt was supported at a supported amount of 3 g per liter of apparent volume of the catalyst support substrate. This Pt burns particulates as a catalyst component.
そして、50g/LでBaを含むBa酢酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥、焼成した。焼成は、500℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり13.7g(0.1mol)の担持量でBaが担持された。なお、このBaは、フィルタ触媒においてはNOx吸蔵成分としてはたらく。 Then, a Ba acetate aqueous solution containing Ba at 50 g / L was prepared, and the catalyst support base material coated with the slurry was immersed, pulled out, dried and fired. Firing was performed by heating at 500 ° C. for 1 hour. Ba was supported at a supported amount of 13.7 g (0.1 mol) per liter of apparent volume of the catalyst support substrate. This Ba acts as a NOx occlusion component in the filter catalyst.
以上の手順により、実施例2のフィルタ触媒が製造された。 The filter catalyst of Example 2 was manufactured by the above procedure.
(実施例3)
スラリーのアルミナのコート量を75gとした以外は、実施例1と同様にして本実施例のフィルタ触媒を製造した。
(Example 3)
A filter catalyst of this example was manufactured in the same manner as in Example 1 except that the alumina coating amount of the slurry was changed to 75 g.
アルミナ粉末150g、水200gを秤量し、アルミナ粉末を水に投入、攪拌して分散させ、湿式ミリングを施してスラリーを調製した。アルミナ粉末全体を100wt%としたときに、1μm以下の粒径の粒子が77%となっていた。 150 g of alumina powder and 200 g of water were weighed, and the alumina powder was put into water, stirred and dispersed, and wet milling was performed to prepare a slurry. When the entire alumina powder was 100 wt%, particles having a particle size of 1 μm or less were 77%.
スラリーを実施例1において用いられたものと同じ触媒担体基材にコートした。スラリーの触媒担体基材へのコートは、スラリー中に触媒担体基材を浸漬し、引き出した後に過剰なスラリーを除去した後に、乾燥、焼成することで行われた。なお、本実施例において過剰なスラリーの除去は、両端の圧力差が10kPaとなるようにした状態で5〜30秒間保持してスラリーを吸引し、その後、他方の端部側を常圧に戻し5〜30秒間保持する圧力変動を繰り返すことでなされた。この圧力変動は、触媒担体基材に塗布されたスラリーが所定の重量となるまで繰り返された。なお、本実施例の製造時には、圧力変動は4回であった。また、焼成は、500℃で1時間加熱することで行われた。 The slurry was coated on the same catalyst support substrate used in Example 1. The coating of the slurry on the catalyst carrier substrate was performed by immersing the catalyst carrier substrate in the slurry, removing the excess slurry after drawing, and then drying and firing. In this embodiment, the excess slurry is removed by holding the slurry for 5 to 30 seconds in a state where the pressure difference between both ends is 10 kPa, and then returning the other end to the normal pressure. This was done by repeating the pressure fluctuation held for 5-30 seconds. This pressure fluctuation was repeated until the slurry applied to the catalyst carrier substrate reached a predetermined weight. In addition, the pressure fluctuation was 4 times at the time of manufacture of a present Example. Moreover, baking was performed by heating at 500 degreeC for 1 hour.
スラリーがコートされた触媒担体基材の重さを測定したところ、スラリーのコート前より2.6g増加していた。すなわち、触媒担体基材の見かけの容積1リットルあたり75gの担持量でアルミナが担持された。 When the weight of the catalyst-support substrate coated with the slurry was measured, it was increased by 2.6 g from before the slurry was coated. That is, alumina was loaded at a loading amount of 75 g per liter apparent volume of the catalyst carrier substrate.
そして、1.5g/LでPtを含むPt硝酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥した。乾燥は、350℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり3gの担持量でPtが担持された。このPtは、触媒成分としてパティキュレートの燃焼をおこなう。 Then, a Pt nitrate aqueous solution containing Pt at 1.5 g / L was prepared, and the catalyst carrier base material coated with the slurry was immersed, pulled out, and dried. Drying was performed by heating at 350 ° C. for 1 hour. Pt was supported at a supported amount of 3 g per liter of apparent volume of the catalyst support substrate. This Pt burns particulates as a catalyst component.
そして、50g/LでBaを含むBa酢酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥、焼成した。焼成は、500℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり13.7g(0.1mol)の担持量でBaが担持された。なお、このBaは、フィルタ触媒においてはNOx吸蔵成分としてはたらく。 Then, a Ba acetate aqueous solution containing Ba at 50 g / L was prepared, and the catalyst support base material coated with the slurry was immersed, pulled out, dried and fired. Firing was performed by heating at 500 ° C. for 1 hour. Ba was supported at a supported amount of 13.7 g (0.1 mol) per liter of apparent volume of the catalyst support substrate. This Ba acts as a NOx occlusion component in the filter catalyst.
以上の手順により、実施例3のフィルタ触媒が製造された。 The filter catalyst of Example 3 was manufactured by the above procedure.
(比較例1)
アルミナ粉末150g、水200gを秤量し、アルミナ粉末を水に投入、攪拌して分散させ、湿式ミリングを施してスラリーを調製した。アルミナ粉末全体を100wt%としたときに、1μm以下の粒径の粒子が77%となっていた。
(Comparative Example 1)
150 g of alumina powder and 200 g of water were weighed, and the alumina powder was put into water, stirred and dispersed, and wet milling was performed to prepare a slurry. When the entire alumina powder was 100 wt%, particles having a particle size of 1 μm or less were 77%.
スラリーを実施例1において用いられたものと同じ触媒担体基材にコートした。スラリーの触媒担体基材へのコートは、コーティングスラリー中に触媒担体基材を浸漬し、引き出した後に過剰なスラリーを除去した後に、乾燥、焼成することで行われた。なお、本比較例において過剰なスラリーの除去は、加圧されたエアーをセル内に吹き付けるエアーブローを繰り返すことでなされた。このエアーブローは、触媒担体基材に塗布されたスラリーが所定の重量となるまで繰り返された。なお、本比較例の製造時には、エアーブローは3回であった。また、焼成は、500℃で1時間加熱することで行われた。 The slurry was coated on the same catalyst support substrate used in Example 1. The coating of the slurry on the catalyst support substrate was performed by immersing the catalyst support substrate in the coating slurry, removing the excess slurry after drawing, and then drying and firing. In this comparative example, the excess slurry was removed by repeating air blowing to blow pressurized air into the cell. This air blow was repeated until the slurry applied to the catalyst carrier substrate reached a predetermined weight. In addition, the air blow was 3 times at the time of manufacture of this comparative example. Moreover, baking was performed by heating at 500 degreeC for 1 hour.
スラリーがコートされた触媒担体基材の重さを測定したところ、触媒担体基材の見かけの容積1リットルあたり150gの担持量でアルミナが担持された。 When the weight of the catalyst carrier substrate coated with the slurry was measured, alumina was loaded at a loading amount of 150 g per liter apparent volume of the catalyst carrier substrate.
そして、1.5g/LでPtを含むPt硝酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥した。乾燥は、350℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり3gの担持量でPtが担持された。このPtは、触媒成分としてパティキュレートの燃焼をおこなう。 Then, a Pt nitrate aqueous solution containing Pt at 1.5 g / L was prepared, and the catalyst carrier base material coated with the slurry was immersed, pulled out, and dried. Drying was performed by heating at 350 ° C. for 1 hour. Pt was supported at a supported amount of 3 g per liter of apparent volume of the catalyst support substrate. This Pt burns particulates as a catalyst component.
そして、50g/LでBaを含むBa酢酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥、焼成した。焼成は、500℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり13.7g(0.1mol)の担持量でBaが担持された。なお、このBaは、フィルタ触媒においてはNOx吸蔵成分としてはたらく。 Then, a Ba acetate aqueous solution containing Ba at 50 g / L was prepared, and the catalyst support base material coated with the slurry was immersed, pulled out, dried and fired. Firing was performed by heating at 500 ° C. for 1 hour. Ba was supported at a supported amount of 13.7 g (0.1 mol) per liter of apparent volume of the catalyst support substrate. This Ba acts as a NOx occlusion component in the filter catalyst.
以上の手順により、比較例1のフィルタ触媒が製造された。 With the above procedure, the filter catalyst of Comparative Example 1 was produced.
(比較例2)
アルミナ粉末150g、水200gを秤量し、アルミナ粉末を水に投入、攪拌して分散させ、湿式ミリングを施してスラリーを調製した。アルミナ粉末全体を100wt%としたときに、1μm以下の粒径の粒子が10%となっていた。
(Comparative Example 2)
150 g of alumina powder and 200 g of water were weighed, and the alumina powder was put into water, stirred and dispersed, and wet milling was performed to prepare a slurry. When the entire alumina powder was 100 wt%, particles having a particle size of 1 μm or less were 10%.
スラリーを実施例1において用いられたものと同じ触媒担体基材にコートした。スラリーの触媒担体基材へのコートは、スラリー中に触媒担体基材を浸漬し、引き出した後に過剰なスラリーを除去し後に、乾燥、焼成することで行われた。なお、本比較例において過剰なスラリーの除去は、比較例1と同様のエアーブローを繰り返すことでなされた。このエアーブローは、触媒担体基材に塗布されたスラリーが所定の重量となるまで繰り返された。なお、本比較例の製造時には、エアーブローは3回であった。また、焼成は、500℃で1時間加熱することで行われた。 The slurry was coated on the same catalyst support substrate used in Example 1. The coating of the slurry on the catalyst carrier substrate was performed by immersing the catalyst carrier substrate in the slurry, removing the excess slurry after drawing, and then drying and firing. In this comparative example, excess slurry was removed by repeating the same air blow as in comparative example 1. This air blow was repeated until the slurry applied to the catalyst carrier substrate reached a predetermined weight. In addition, the air blow was 3 times at the time of manufacture of this comparative example. Moreover, baking was performed by heating at 500 degreeC for 1 hour.
スラリーがコートされた触媒担体基材の重さを測定したところ、触媒担体基材の見かけの容積1リットルあたり150gの担持量でアルミナが担持された。 When the weight of the catalyst carrier substrate coated with the slurry was measured, alumina was loaded at a loading amount of 150 g per liter apparent volume of the catalyst carrier substrate.
そして、1.5g/LでPtを含むPt硝酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥した。乾燥は、350℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり3gの担持量でPtが担持された。このPtは、触媒成分としてパティキュレートの燃焼をおこなう。 Then, a Pt nitrate aqueous solution containing Pt at 1.5 g / L was prepared, and the catalyst carrier base material coated with the slurry was immersed, pulled out, and dried. Drying was performed by heating at 350 ° C. for 1 hour. Pt was supported at a supported amount of 3 g per liter of apparent volume of the catalyst support substrate. This Pt burns particulates as a catalyst component.
そして、50g/LでBaを含むBa酢酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥、焼成した。焼成は、500℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり13.7g(0.1mol)の担持量でBaが担持された。なお、このBaは、フィルタ触媒においてはNOx吸蔵成分としてはたらく。 Then, a Ba acetate aqueous solution containing Ba at 50 g / L was prepared, and the catalyst support base material coated with the slurry was immersed, pulled out, dried and fired. Firing was performed by heating at 500 ° C. for 1 hour. Ba was supported at a supported amount of 13.7 g (0.1 mol) per liter of apparent volume of the catalyst support substrate. This Ba acts as a NOx occlusion component in the filter catalyst.
以上の手順により、比較例2のフィルタ触媒が製造された。 The filter catalyst of Comparative Example 2 was manufactured by the above procedure.
(比較例3)
アルミナ粉末75g、水200gを秤量し、アルミナ粉末を水に投入、攪拌して分散させ、湿式ミリングを施してスラリーを調製した。アルミナ粉末全体を100wt%としたときに、1μm以下の粒径の粒子が77%となっていた。
(Comparative Example 3)
75 g of alumina powder and 200 g of water were weighed, and the alumina powder was put into water, stirred and dispersed, and wet milled to prepare a slurry. When the entire alumina powder was 100 wt%, particles having a particle size of 1 μm or less were 77%.
スラリーを実施例1において用いられたものと同じ触媒担体基材にコートした。スラリーの触媒担体基材へのコートは、スラリー中に触媒担体基材を浸漬し、引き出した後に過剰なスラリーを除去した後に、乾燥、焼成することで行われた。なお、本比較例において過剰なスラリーの除去は、比較例1と同様のエアーブローを繰り返すことでなされた。このエアーブローは、触媒担体基材に塗布されたスラリーが所定の重量となるまで繰り返された。なお、本比較例の製造時には、エアーブローは4回であった。また、焼成は、500℃で1時間加熱することで行われた。 The slurry was coated on the same catalyst support substrate used in Example 1. The coating of the slurry on the catalyst carrier substrate was performed by immersing the catalyst carrier substrate in the slurry, removing the excess slurry after drawing, and then drying and firing. In this comparative example, excess slurry was removed by repeating the same air blow as in comparative example 1. This air blow was repeated until the slurry applied to the catalyst carrier substrate reached a predetermined weight. In addition, the air blow was 4 times at the time of manufacture of this comparative example. Moreover, baking was performed by heating at 500 degreeC for 1 hour.
スラリーがコートされた触媒担体基材の重さを測定したところ、触媒担体基材の見かけの容積1リットルあたり75gの担持量でアルミナが担持された。 When the weight of the catalyst carrier substrate coated with the slurry was measured, alumina was loaded at a loading amount of 75 g per liter of apparent volume of the catalyst carrier substrate.
そして、1.5g/LでPtを含むPt硝酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥した。乾燥は、350℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり3gの担持量でPtが担持された。このPtは、触媒成分としてパティキュレートの燃焼をおこなう。 Then, a Pt nitrate aqueous solution containing Pt at 1.5 g / L was prepared, and the catalyst carrier base material coated with the slurry was immersed, pulled out, and dried. Drying was performed by heating at 350 ° C. for 1 hour. Pt was supported at a supported amount of 3 g per liter of apparent volume of the catalyst support substrate. This Pt burns particulates as a catalyst component.
そして、50g/LでBaを含むBa酢酸塩水溶液を調製し、スラリーがコートされた触媒担体基材を浸漬し、引き出した後に乾燥、焼成した。焼成は、500℃で1時間加熱することで行われた。触媒担体基材の見かけの容積1リットルあたり13.7g(0.1mol)の担持量でBaが担持された。なお、このBaは、フィルタ触媒においてはNOx吸蔵成分としてはたらく。 Then, a Ba acetate aqueous solution containing Ba at 50 g / L was prepared, and the catalyst support base material coated with the slurry was immersed, pulled out, dried and fired. Firing was performed by heating at 500 ° C. for 1 hour. Ba was supported at a supported amount of 13.7 g (0.1 mol) per liter of apparent volume of the catalyst support substrate. This Ba acts as a NOx occlusion component in the filter catalyst.
以上の手順により、比較例3のフィルタ触媒が製造された。 The filter catalyst of Comparative Example 3 was manufactured by the above procedure.
(評価)
実施例および比較例のフィルタ触媒の細孔構造を水銀ポロシメータ(島津製作所製、商品名:オートポアー9200)を用いて測定した。測定結果を表1に示した。なお、細孔構造の測定における水銀ポロシメータの操作は、0〜200MPaの間で水銀圧入圧力を上昇させていくことで行われた。
(Evaluation)
The pore structures of the filter catalysts of Examples and Comparative Examples were measured using a mercury porosimeter (manufactured by Shimadzu Corporation, trade name: Autopore 9200). The measurement results are shown in Table 1. In addition, operation of the mercury porosimeter in the measurement of the pore structure was performed by increasing the mercury intrusion pressure between 0 and 200 MPa.
表1において示された実施例および比較例のフィルタ触媒の気孔率を20μm以下と20μm以上で分け、図2および3に示した。図2には1〜20μmの細孔径の気孔率を、図3には20〜70μmの細孔径の気孔率を示した。 The porosity of the filter catalysts of Examples and Comparative Examples shown in Table 1 are divided into 20 μm or less and 20 μm or more, and are shown in FIGS. FIG. 2 shows the porosity with a pore diameter of 1 to 20 μm, and FIG. 3 shows the porosity with a pore diameter of 20 to 70 μm.
表1および両図から、各実施例のフィルタ触媒は1〜20μmの径の細孔が多く存在し、20〜70μmの径の細孔が少ないことがわかる。また、実施例3のフィルタ触媒のように、触媒層の担持量(スラリーのコート量)を少なくしても、1〜20μmの径の細孔が多く存在している。 From Table 1 and both figures, it can be seen that the filter catalyst of each Example has many pores having a diameter of 1 to 20 μm and few pores having a diameter of 20 to 70 μm. Further, as in the filter catalyst of Example 3, there are many pores having a diameter of 1 to 20 μm even if the amount of catalyst layer supported (slurry coating amount) is reduced.
具体的には、各実施例のフィルタ触媒は、図4に示したように、触媒担体基材の細孔の大きさによらずに、細孔の内部にまで均一な厚さの触媒層が形成されている。これにより、触媒担体基材の1〜20μmの径の細孔は触媒層により細孔径が小さくなり、触媒担体基材の20μm以上の径の細孔は触媒層により細孔径が小さくなり20μm以下の径の細孔となった。 Specifically, as shown in FIG. 4, the filter catalyst of each example has a catalyst layer having a uniform thickness up to the inside of the pores regardless of the size of the pores of the catalyst support substrate. Is formed. As a result, the pores having a diameter of 1 to 20 μm of the catalyst support substrate are reduced in pore size by the catalyst layer, and the pores having a diameter of 20 μm or more in the catalyst support substrate are reduced by the catalyst layer to be 20 μm or less. It became the pore of the diameter.
これに対して、各比較例のフィルタ触媒は、1〜20μmの径の細孔が少なく、かつ20〜70μmの径の細孔が多く存在している。 On the other hand, the filter catalyst of each comparative example has few pores having a diameter of 1 to 20 μm and many pores having a diameter of 20 to 70 μm.
具体的には、比較例1および3のフィルタ触媒は、図5に示したように、触媒担体基材の1〜20μmの径の細孔は触媒層により細孔が閉塞し、触媒担体基材の20μm以上の径の細孔は触媒層が薄く20μm以上の径の細孔として残存した。さらに、比較例2のフィルタ触媒は、図6に示したように、触媒担体基材の1〜20μmの径の細孔はその開口部に形成された触媒層により細孔が閉塞し、触媒担体基材の20μm以上の径の細孔はその開口部に触媒層が存在するが20μm以上の径の細孔として残存した。なお、図5および図6は、図4のセル壁の拡大断面図と同じ断面を示した図である。 Specifically, in the filter catalysts of Comparative Examples 1 and 3, as shown in FIG. 5, the pores having a diameter of 1 to 20 μm of the catalyst carrier substrate are blocked by the catalyst layer, and the catalyst carrier substrate The pores having a diameter of 20 μm or more remained as thin pores having a diameter of 20 μm or more. Further, in the filter catalyst of Comparative Example 2, as shown in FIG. 6, the pores having a diameter of 1 to 20 μm of the catalyst carrier substrate are blocked by the catalyst layer formed in the opening portion, and the catalyst carrier The pores having a diameter of 20 μm or more in the substrate remained as pores having a diameter of 20 μm or more, although a catalyst layer was present in the opening. 5 and 6 are views showing the same cross section as the enlarged cross sectional view of the cell wall in FIG.
(圧損の測定)
つづいて、実施例および比較例のフィルタ触媒の圧損の測定を行った。
(Measurement of pressure loss)
Subsequently, the pressure loss of the filter catalysts of Examples and Comparative Examples was measured.
まず、排気量が2リットルの加給式直噴ディーゼルエンジンを有する車両の排気系にフィルタ触媒を設置した。そして、2000rpmの回転数でトルクが30N・mの定常運転を2時間行った。この定常運転によりフィルタ触媒の見かけの容積1リットルあたり4gのパティキュレートが堆積した。その後、パティキュレートが堆積したフィルタ触媒を取り出し、窒素ガスを流すことができるモデルガス装置に設置して、100℃に加熱した窒素ガスを1分あたり30リットルの流量で流し、フィルタ触媒の前後の圧力センサの測定値から圧損を測定し、測定結果を図7に示した。なお、圧損は、フィルタ触媒の前後の二つの圧力センサにおいて測定された圧力の差から求めた。 First, a filter catalyst was installed in the exhaust system of a vehicle having a supply type direct injection diesel engine with a displacement of 2 liters. Then, a steady operation was performed for 2 hours at a rotational speed of 2000 rpm and a torque of 30 N · m. By this steady operation, 4 g of particulates were deposited per liter of apparent volume of the filter catalyst. Thereafter, the filter catalyst on which the particulates are deposited is taken out and installed in a model gas apparatus capable of flowing nitrogen gas. Nitrogen gas heated to 100 ° C. is flowed at a flow rate of 30 liters per minute. The pressure loss was measured from the measured value of the pressure sensor, and the measurement result is shown in FIG. In addition, the pressure loss was calculated | required from the difference of the pressure measured in two pressure sensors before and behind a filter catalyst.
図7より、各実施例のフィルタ触媒は、各比較例のフィルタ触媒と比較して圧損が低くなっていることが確認された。すなわち、各実施例のフィルタ触媒は、細孔が連続してなる排気ガスが通過する連通孔が残存している。これに対して、各比較例のフィルタ触媒は、連通孔が触媒層により閉塞し、さらに堆積したパティキュレートが連通孔を閉塞させて圧損を上昇させている。 From FIG. 7, it was confirmed that the pressure loss of the filter catalyst of each Example was lower than that of the filter catalyst of each Comparative Example. That is, in the filter catalyst of each example, the communication hole through which the exhaust gas having continuous pores passes remains. On the other hand, in the filter catalyst of each comparative example, the communication holes are blocked by the catalyst layer, and the accumulated particulates block the communication holes to increase the pressure loss.
上記各実施例のフィルタ触媒は、パティキュレートの堆積による圧損の上昇が小さいことから、ディーゼルエンジンに高い負荷をかけることなくパティキュレートを捕捉することができる。このため、より多くの量のパティキュレートを捕捉、処理できる効果を有する。 Since the filter catalyst of each of the above embodiments has a small increase in pressure loss due to accumulation of particulates, the particulates can be captured without applying a high load to the diesel engine. For this reason, it has the effect that a larger amount of particulates can be captured and processed.
1…触媒担体基材
2…封止されたセル
3…開口したセル
DESCRIPTION OF
Claims (2)
1〜20μmの細孔を11%以上の気孔率で有することを特徴とするフィルタ触媒。 In a filter catalyst having a catalyst support substrate made of a heat-resistant porous body having continuous pores, and a catalyst layer for burning particulates formed on the surface of the catalyst support substrate,
A filter catalyst having 1 to 20 μm pores with a porosity of 11% or more.
該スラリーに分散した粉末の全体量を100wt%としたときに、1μm以下の粒径の耐熱性酸化物粉末が70wt%以上で含まれる請求項1記載のフィルタ触媒。 The catalyst layer has a support layer formed by preparing a slurry of heat-resistant oxide powder, coating the slurry on the catalyst support substrate, drying, and firing;
2. The filter catalyst according to claim 1, wherein the heat-resistant oxide powder having a particle diameter of 1 μm or less is contained in an amount of 70 wt% or more when the total amount of powder dispersed in the slurry is 100 wt%.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004033924A JP4429756B2 (en) | 2004-02-10 | 2004-02-10 | Filter catalyst |
US10/587,984 US7622419B2 (en) | 2004-02-10 | 2005-02-10 | Filter catalyst |
PCT/JP2005/002656 WO2005075053A1 (en) | 2004-02-10 | 2005-02-10 | Filter catalyst |
EP05710438A EP1723998B1 (en) | 2004-02-10 | 2005-02-10 | Filter catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004033924A JP4429756B2 (en) | 2004-02-10 | 2004-02-10 | Filter catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005224667A JP2005224667A (en) | 2005-08-25 |
JP4429756B2 true JP4429756B2 (en) | 2010-03-10 |
Family
ID=34836154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004033924A Expired - Lifetime JP4429756B2 (en) | 2004-02-10 | 2004-02-10 | Filter catalyst |
Country Status (4)
Country | Link |
---|---|
US (1) | US7622419B2 (en) |
EP (1) | EP1723998B1 (en) |
JP (1) | JP4429756B2 (en) |
WO (1) | WO2005075053A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2243801A1 (en) | 2009-03-03 | 2010-10-27 | Asahi Glass Company Limited | Resin substrate provided with coating layer |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5142532B2 (en) * | 2004-11-26 | 2013-02-13 | イビデン株式会社 | Honeycomb structure |
WO2007026844A1 (en) * | 2005-08-31 | 2007-03-08 | Ngk Insulators, Ltd. | Honeycomb catalytic structure, precoated support for producing honeycomb catalytic structure, and process for producing honeycomb catalytic structure |
US8119075B2 (en) * | 2005-11-10 | 2012-02-21 | Basf Corporation | Diesel particulate filters having ultra-thin catalyzed oxidation coatings |
JP5215634B2 (en) | 2007-11-07 | 2013-06-19 | 本田技研工業株式会社 | Exhaust gas purification device |
JP4753209B2 (en) | 2007-12-06 | 2011-08-24 | 本田技研工業株式会社 | Oxidation catalyst equipment for exhaust gas purification |
JP2009136787A (en) * | 2007-12-06 | 2009-06-25 | Honda Motor Co Ltd | Method of manufacturing oxidation catalyst device for purification of exhaust gas |
EP2230013A1 (en) * | 2008-04-25 | 2010-09-22 | Honda Motor Co., Ltd. | Production method of oxidation catalyst device for exhaust gas purificatiion |
JP5519181B2 (en) * | 2009-05-13 | 2014-06-11 | 本田技研工業株式会社 | Exhaust gas purification device for internal combustion engine |
JP6542690B2 (en) * | 2016-02-12 | 2019-07-10 | トヨタ自動車株式会社 | Method for producing filter catalyst |
JP6546366B1 (en) * | 2017-09-21 | 2019-07-17 | 株式会社キャタラー | Exhaust gas purification catalyst |
Family Cites Families (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1260909A (en) * | 1985-07-02 | 1989-09-26 | Koichi Saito | Exhaust gas cleaning catalyst and process for production thereof |
US5075274A (en) * | 1989-03-15 | 1991-12-24 | Kabushiki Kaisha Riken | Exhaust gas cleaner |
US5254519A (en) * | 1990-02-22 | 1993-10-19 | Engelhard Corporation | Catalyst composition containing platinum and rhodium components |
US6869573B2 (en) * | 1990-11-09 | 2005-03-22 | Ngk Insulators, Ltd. | Heater and catalytic converter |
GB2256375B (en) * | 1991-05-31 | 1995-06-07 | Riken Kk | Exhaust gas cleaner and method of cleaning exhaust gas |
CA2124441A1 (en) * | 1991-11-26 | 1993-06-10 | Robert J. Farrauto | Ceria-alumina oxidation catalyst and method of use |
US5376610A (en) * | 1992-04-15 | 1994-12-27 | Nissan Motor Co., Ltd. | Catalyst for exhaust gas purification and method for exhaust gas purification |
US5217939A (en) * | 1992-05-11 | 1993-06-08 | Scientific Design Company, Inc. | Catalyst for the prduction of nitric acid by oxidation of ammonia |
JP3285614B2 (en) * | 1992-07-30 | 2002-05-27 | 日本碍子株式会社 | Exhaust gas purification catalyst and method for producing the same |
JP3281087B2 (en) * | 1993-02-10 | 2002-05-13 | 日本碍子株式会社 | Exhaust gas purification catalyst |
FR2715580B1 (en) * | 1994-01-31 | 1996-04-05 | Inst Francais Du Petrole | Catalyst for treating exhaust gases from internal combustion engines. |
US6667018B2 (en) * | 1994-07-05 | 2003-12-23 | Ngk Insulators, Ltd. | Catalyst-adsorbent for purification of exhaust gases and method for purification of exhaust gases |
FR2729090A1 (en) * | 1995-01-11 | 1996-07-12 | Inst Francais Du Petrole | CATALYSTS FOR SELECTIVE REDUCTION OF NITROGEN NITROGEN OXIDES IN OXIDIZING MEDIA, PROCESS FOR PREPARATION AND USE |
JP3750178B2 (en) | 1995-04-05 | 2006-03-01 | 株式会社デンソー | Exhaust gas purification filter and manufacturing method thereof |
JP3707843B2 (en) | 1995-12-08 | 2005-10-19 | 株式会社日本自動車部品総合研究所 | Diesel exhaust gas purification filter |
JPH09173866A (en) | 1995-12-28 | 1997-07-08 | Nippon Soken Inc | Diesel exhaust gas purifying filter |
JP3560408B2 (en) * | 1996-02-15 | 2004-09-02 | 株式会社日本自動車部品総合研究所 | Diesel exhaust gas purification filter and method for producing the same |
JP3874443B2 (en) * | 1996-04-12 | 2007-01-31 | 株式会社日本自動車部品総合研究所 | Particulate collection filter |
US5830421A (en) * | 1996-07-03 | 1998-11-03 | Low Emissions Technologies Research And Development Partnership | Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process |
US6921738B2 (en) * | 1996-12-06 | 2005-07-26 | Engelhard Corporation | Catalytic metal plate |
JPH10180041A (en) * | 1996-12-20 | 1998-07-07 | Ngk Insulators Ltd | Catalyst for purification of exhaust gas and exhaust gas purifying system |
JPH10180099A (en) * | 1996-12-20 | 1998-07-07 | Ngk Insulators Ltd | Catalyst for purifying waste gas and waste gas purifying system |
EP1020223A3 (en) * | 1999-01-12 | 2001-09-12 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Porous material and production process thereof, catalyst comprising the porous material and process for purifying exhaust gas |
JP3978759B2 (en) | 1999-01-18 | 2007-09-19 | 日産自動車株式会社 | Method and apparatus for coating catalyst slurry on ceramic monolith support |
JP5106716B2 (en) | 2000-01-05 | 2012-12-26 | パナソニック株式会社 | Exhaust gas purification material and exhaust gas purification device |
JP2001314762A (en) * | 2000-05-11 | 2001-11-13 | Ngk Insulators Ltd | Catalyst for cleaning exhaust gas |
US6750168B2 (en) * | 2000-12-05 | 2004-06-15 | Delphi Technologies, Inc. | High-temperature aging tolerance catalyzed adsorber system for treating internal combustion engine exhaust gas |
JP2002295228A (en) | 2001-03-30 | 2002-10-09 | Ibiden Co Ltd | Filter for cleaning exhaust gas |
JP4715032B2 (en) * | 2001-05-25 | 2011-07-06 | トヨタ自動車株式会社 | Diesel exhaust gas purification filter |
JP4174976B2 (en) | 2001-06-01 | 2008-11-05 | 日産自動車株式会社 | Exhaust purification device and method for manufacturing the same |
JP4007058B2 (en) | 2001-08-06 | 2007-11-14 | 株式会社デンソー | Exhaust gas purification filter |
US6827754B2 (en) | 2001-09-13 | 2004-12-07 | Hitachi Metals, Ltd. | Ceramic honeycomb filter |
JP3871197B2 (en) | 2001-11-27 | 2007-01-24 | トヨタ自動車株式会社 | Particulate filter |
JP3872384B2 (en) * | 2002-06-13 | 2007-01-24 | トヨタ自動車株式会社 | Exhaust gas purification filter catalyst |
JP3855267B2 (en) | 2002-06-17 | 2006-12-06 | トヨタ自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
JP3874270B2 (en) * | 2002-09-13 | 2007-01-31 | トヨタ自動車株式会社 | Exhaust gas purification filter catalyst and method for producing the same |
-
2004
- 2004-02-10 JP JP2004033924A patent/JP4429756B2/en not_active Expired - Lifetime
-
2005
- 2005-02-10 US US10/587,984 patent/US7622419B2/en not_active Expired - Fee Related
- 2005-02-10 WO PCT/JP2005/002656 patent/WO2005075053A1/en not_active Application Discontinuation
- 2005-02-10 EP EP05710438A patent/EP1723998B1/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2243801A1 (en) | 2009-03-03 | 2010-10-27 | Asahi Glass Company Limited | Resin substrate provided with coating layer |
Also Published As
Publication number | Publication date |
---|---|
US20080025882A1 (en) | 2008-01-31 |
EP1723998A1 (en) | 2006-11-22 |
JP2005224667A (en) | 2005-08-25 |
WO2005075053A1 (en) | 2005-08-18 |
US7622419B2 (en) | 2009-11-24 |
EP1723998B1 (en) | 2012-04-18 |
EP1723998A4 (en) | 2007-10-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6016916B2 (en) | Diesel particulate filter and exhaust gas purification device | |
JP4907860B2 (en) | Filter catalyst | |
JP5993009B2 (en) | Diesel particulate filter and exhaust gas purification device | |
US7625529B2 (en) | Catalyst-carrying filter | |
JP4284588B2 (en) | Exhaust gas purification filter catalyst | |
JP3874270B2 (en) | Exhaust gas purification filter catalyst and method for producing the same | |
EP1723998B1 (en) | Filter catalyst | |
JP2007144371A (en) | Catalyst for cleaning exhaust gas and its manufacturing method | |
JP7228065B2 (en) | Catalyst-coated gasoline particulate filter and its manufacturing method | |
US20060287193A1 (en) | Process for producing a filter catalyst | |
JP2009160547A (en) | Exhaust-gas cleaning catalyst and its production method | |
JP3855267B2 (en) | Exhaust gas purification catalyst and method for producing the same | |
JP2009233582A (en) | Honeycomb catalyst body | |
JP4420655B2 (en) | Particulate filter catalyst and method for producing the same | |
JP2006231116A (en) | Exhaust gas-cleaning filter catalyst | |
JP2005248726A (en) | Filter catalyst for exhaust emission control | |
JP5146752B2 (en) | Method for producing exhaust gas purification catalyst | |
JP4545857B2 (en) | Catalyst and method for producing the same | |
JP2001314764A (en) | Catalyst and its manufacturing method | |
JP2007190459A (en) | Catalyst for pm purification | |
JP2007136357A (en) | Manufacturing method of catalyst for purification of exhaust gas | |
JP2009247995A (en) | Exhaust gas cleaning catalyst and production method thereof | |
CN112218718B (en) | Exhaust gas purifying catalyst | |
JP4526276B2 (en) | Method for analyzing filter catalyst and catalyst layer thereof | |
JP2006159020A (en) | Filter and catalyst for purification of exhaust gas |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061017 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090915 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091112 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20091208 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091216 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121225 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4429756 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121225 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131225 Year of fee payment: 4 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |